Extraction of boron from aqueous solutions with salicylic acid derivatives and isoamyl alcohol

ABSTRACT

A process for extracting boron from aqueous boron containing solutions by contacting the aqueous solution with a substantially water immiscible salicylic acid derivative or a salt thereof, nuclear substituted with an alkyl, aryl, alkaryl, or cycloakyl radical wherein the derivative has at least 11 carbon atoms in a water immiscible solvent comprising isoamyl alcohol in the range of from 10 to 100 percent by volume. Preferably, the balance of the solvent is an inexpensive water immiscible petroleum cut. Boron is sequestered by the salicylic acid derivative and the isoamyl alcohol has a synergistic effect in enhancing the proportion of boron extracted.

United States Patent [191 Grannen EXTRACTION OF BORON FROM AQUEOUSSOLUTIONS WITH SALICYLIC ACID DERIVATIVES AND ISOAMYL ALCOHOL [76]lnventor: Edward A. Grannen, 1431 Isabelita Ct., Upland, Calif. 91786 22Filed: Mar. 16, 1973 21 Appl. No.: 342,076

Related U.S. Application Data [62] Division of Ser. No. 175,007, Aug.25, 1971.

OTHER PUBLICATIONS Chemical Abstracts, American Chemical Soc., Vol.

[451 Oct. 1, 1974 67, (1967), 94,462K and 111,844f.

Primary Examiner-Leland A. Sebastian Assistant Examiner-lrwin GluckAttorney, Agent, or Firm-Christie, Parker & Hale [57] ABSTRACT A processfor extracting boron from aqueous boron containing solutions bycontacting the aqueous solution with a substantially water immisciblesalicylic acid derivative or a salt thereof, nuclear substituted with analkyl, aryl, alkaryl, 0r cycloakyl radical wherein the derivative has atleast 11 carbon atoms in a water immiscible solvent comprising isoamylalcohol in the range of from 10 to 100 percent by volume. Preferably,the balance of the solvent is an inexpensive water immiscible petroleumcut. Boron is sequestered by the salicylic acid derivative and theisoamyl alcohol has a synergistic effect in enhancing the proportion ofboron extracted.

10 Claims, No Drawings CROSS REFERENCE TO RELATED APPLICATIONS This is adivision, of U.S. Pat. application Ser. No. 175,007, filed Aug. 25,1971, now U.S. Pat. No. 3,812,238.

BACKGROUND This application comprises an improvement on copending U.S.Pat. application Ser. No. 172,904 now U.S. Pat. No. 3,741,731 entitledExtraction of Boron From Aqueous Solutions with Salicylic AcidDerivatives," by Willard D. Peterson and assigned to OccidentalPetroleum Corporation, assignee of this application. A number ofsuitable salicylic acid derivatives are set forth specifically thereinalong with details of processes for synthesizing and using suchderivatives. The teachings of this copending application are herebyincorpo rated by reference for full force and effect as if set forth infull herein.

It is often desirable to remove boron from natural or artificial watersand brines both for purification purposes and for recovery of thevaluable boron. Thus, for example, in some areas large amounts of waterare not suitable for irrigation because the boron content exceeds two orthree parts per million, which is the tolera ble limit for citrus andsome other agricultural crops. Large scale economical removal of boronfrom such dilute solutions is desirable. Similarly, boron contaminationis commonly present in magnesium chloride brines, and it interferes withsubsequent production of magnesium metal'by way of electrowinningoperations. Many brines contain a sufficient boron concentration thatboric acid can economically be recovered therefrom.

A variety of ion exchange systems have been employed for extractingboron values from aqueous solutions. Solid ion exchange resins havecertain technical.

difficulties in handling large volumes of solutions because of therelatively low sequestering rates that may be present and, further,there are problems of contamination of ion exchange resins byparticulate matter and the like.

Another technique for removing boron-values from dilute aqueoussolutions and brines is by liquid-liquid extraction wherein the aqueousphase is contacted by a water immiscible organic phase containing amaterial with which the boron is complexed so as to partitionprincipally to the organic phase instead of the aqueous phase. The borondepleted aqueous phase and boron containing organic phase are separatedso that the boron can be extracted therefrom by contacting the organicphase with a strong acid or strong base as may be desired. A number oforganic extracting agents have been employed for extracting boron valuesfrom aqueous solutions, including aliphatic diols or other diols,catechols, and certain aliphatic alcohols. The use of isoamyl alcohol toextract boron from aqueous solution is mentioned in Chemical Abstracts67 94462, referencing Zh. Neorg. Khim 12, 1624 (1967), and in ChemicalAbstracts 67 l l 1844, referencing Zh. Neorg. Khim 12, 1930 (1967). Inthe aforementioned copending patent application a number of nuclearsubstituted salicylic acid derivatives for extraction of boron fromdilute aqueous solutions are described in detail. In this process aswell as other extraction processes, it is important for economic reasonsto extract as much boron as possible into the water immiscible organicphase so that the number of sequential contacts between the organicphase and the aqueous phase can be reduced. The quantity of boron thatis removed can be increased by increasing the total volume of organicphase with consequent cost increases; however, it is preferable toenhance the distribution coefficient between the organic and aqueousphases so that a larger quantity of boron is contained in a smallervolume of organic phase. This not only reduces the number of sequentialcontactings for complete extraction, but also decreases the capital costrequired for an economical boron extraction plant.

BRIEF SUMMARY OF THE INVENTION Therefore, in practice of this inventionaccording to a presently preferred embodiment there is provided acomposition comprising a substantially water immiscible nuclearsubstituted salicylic acid derivative having i 9r1 .1!lav COOH wherein Rand R are radicals selected from the group consisting of hydrogen,halogen, alkyl, aryl, alkaryl, and cycloalkyl radicals having sufficientcarbon atoms that the substituted salicylic acid derivative has at leastll carbon atoms in the molecule in a proportion of from about 0.05 molarto the solubility limit ina water immiscible solvent including isoamylalcohol in the range of from about 10 to percent by volume of thesolvent. The salicylic acid derivative has one radical selected from thegroup'consisting of alkyl, aryl, alkaryl and cycloalkyl groups having atleast three carbon atoms and the other radical is selected from thegroup consisting of hydrogen, halogen and alkyl groups; and encompassesalkali, alkaline earth, ammonium or organic ammonium salts thereof. Aprocess for extracting boron from aqueous solution by contacting theaqueous solution with the above composition is provided.

DESCRIPTION The preferred extraction agent employed in practice of thisinvention is a substantially'water immiscible nuclear substitutedsalicylic acid derivative having the where R and R represent radicalsselected from the class consisting of hydrogen, halogen, alkyl radicals,aryl radicals, alkaryl radicals, cycloalkyl radicals and mixturesthereof; and also alkali, alkaline earth, ammonium and organic ammoniumsalts thereof. For best results, the derivative of salicylic acid has atotalof at least 1 1 carbon atoms in the molecule, and preferably lessthan about 40 carbon atoms. Preferably R and R are substituted in the 3-and 5- positions respectively. Preferably R is selected from the groupconsisting of alkyl, aryl, alkaryl, and cycloalkyl radicals having atleast 3 carbon atoms and R is selected from the group consisting ofhydrogen, halogen, and alkyl groups. The

. salicylic acid derivatives containing a 5- tertiary alkyl group from 8to 12 carbon atoms are particularly preferred.

A few examples of suitable salicylic acid derivatives 25;

include S-tertiary butyl salicylic acid, S-tertiary octyl; salicylicacid, 5-isooctyl salicylic acid, S-tertiary amyli salicylic acid, 5-tertiary nonyl salicylic acid, S-benzyl salicylic acid, 5-cyclohexylsalicylic acid, 3,5-diisopropyl salicylic acid, 3,5-di-tertiary butylsalicylic acid, 3-isobutyl, 5-ethyl salicylic acid, 3-isopropyl-6-methyl salicylic acid, 3-methyl-6-isopropyl salicylic acid, and3,5-di-tertiary dodecyl salicylic acid. A particularly preferredsalicylic acid derivative is S-tertiary octyl salicylic acid which ismore specifically 5- (l,l,3,3-tetramethyl butyl) salicylic acid.

The salicylic acid derivative contains at least 1 1 carbon atoms inorder to have sufficient water immiscibility that only a very smallquantity of the extraction agent is carried away in the boron depletedwater or in the strong acid or base used for stripping the boron fromthe organic phase. When the salicylic acid derivative has less than 1 1carbon atoms it may be sufficiently soluble in water to be uneconomicalfor very largescale operation. Preferably, the salicylic acid derivativehas less than about 40 carbon atoms in the molecule. since suchderivatives can be made from commercially available raw materialswithout excessive cost.

It is particularly preferred that the salicylic acid derivatives containa tertiary alkyl group having from 8 to 12 carbon atoms substituted inthe 5-position, that is, as radical R in the above formula. Suchsalicylic acid derivatives are found to have excellent stability in theorganic carrier solvent as well as excellent water immiscibility so asto remain in the organic phase during the extraction step with a boroncontaining brine, and duringthe stripping step when in contact with astrong acid or base. These materials are stable so that they do notdecompose readily and can be recycled many times. If the derivative hasa radical having less than eight car- ,bon atoms, it may have excessivewater solubility for use in large-scale boron extraction operations. Ifthe salicylic acid derivative has a tertiary alkyl group having morethan about 12 carbon atoms, the expense of the raw materials for makingthe derivative is sufficiently high that the product is not suitable forlargescale operations. The alkali, alkaline earth, ammonium and organicammonium salts of the nuclear substituted sa i yliqasziarsabpssitafiztsrmstisssf hisinvqaf tion, particularly when minimum change inpH is defect wherein the amount of boron extracted from the solution andthe partition coefficient are increased significantly above the valuesobtained for isoamyl alcohol alone or in combination with other organicsolvents, and also as compared with extraction by salicylic acidderivatives in organic solvents in the absence of isoamyl alcohol. 7 W 7The water immiscible phase preferably contains other water immiscibleorganic solvents in addition to the isoamyl alcohol and may includealiphatic hydrocarbons, aromatic hydrocarbons, other aliphatic oraromatic alcohols, phenolics, ethers, chlorocarbons and the like, eitheralone or in the form of mixtures. Ad-

juncts in the organic phase may include water immiscible primary,secondary, and tertiary alkyl amines,

1 cent boiling point of 381 F, and a dry end point of 408 F. AmscoSolvent-G has in excess of 98 percent com- .pounds having eight or morecarbon atoms.

lt ispreferred that the proportion of isoamyl alcohol in the solvent bein the range of from about 10 to 100 percent by volume. If theproportion of isoamyl alcohol is less than about 10 percent, difficultymay be encountered in dissolving a sufficient quantity of nuclearsubstituted salicylic acid derivative for efficient boron extraction.

It is particularly preferred that the isoamyl alcohol be present in therange of from about 25 to percent by volume with the balance being madeup of other substantially water immiscible hydrocarbons. It isparticularly preferred that the other hydrocarbon be an inexpensivearomatic petroleum cut or the like. It is particularly preferred thatthe isoamyl alcohol in the solvent be at least about 25 percent byvolume since a sufficient quantity of boron may be removed thereby, thatthe total volume of organic phase is not excessive and capital costs arethereby reduced. No substantial benelimit of the derivative in theorganic solvent. When the quantity of salicylic acid derivative isreduced below about 0.05 molar, the total quantity of the derivative maybe near the total amount of boron in the water phase, and the extractionefficiency drops off. Typically, the maximum solubility of the preferredsalicylic acid derivatives is 0.4 molar in the aforementioned solvents.

It is particularly preferred that the salicylic acid derivative bepresent in the range of from about 0.05 to 0.1 molar. Excellent resultsare obtained with salicylic acid derivatives employed at about 0.1 molarand no significant increase in extraction efficiency is obtained byfurther increasing the salicylic acid derivative concentration. Further,there is a slight tendency towards forming emulsions of the two phaseswhen the salicylic acid derivative content is higher than about 0.1molar, and the expense of the derivative goes up without concomitantincreased performance. In the preferred range, the concentration of thederivative is easily controlled and good phase separation is obtainedunder substantially all operating conditions.

The organic phase comprising the salicylic acid derivative in the abovedescribed water immiscible carrier is intimately contacted with theboron containing aqueous solution in any suitable conventional manner,such as, for example, by countercurrent flow, stirring, shaking, and thelike.

The volume ratio of organic phase to aqueous phase is preferably in therange of from about 1:50 to :1, or even higher. Phase ratios rangingfrom about 1:10 to 10:1 are generally preferred for most economicalextraction with the least number of extraction steps for completeextraction without significant loss of extraction agent. A relativelyhigh volume ratio of organic phase to aqueous phase is preferablyemployed when the boron concentration in the aqueous solution isrelatively low, or where the highest possible extraction efficiency isdesired.

As is well known, extraction efficiency is enhanced by seriallyperforming the extraction step with organic phase having successivelylower boron concentrations, i.e., by a countercurrent multipleextraction process. The number of repetitions of the process will varydepending on the desired degree of extraction and the original boronconcentration. Contact times between the organic and aqueous phase inexcess of about 1 minute may be required for adequate extraction, and acontact time in the range of from 1 to 5 minutes is preferred.

The extraction is preferably conducted so that the final pH of the borondeficient aqueous solution is between about 0.5 and 9.0. The final pl-ldepends in large part on the nature and concentration of materials otherthan boron in the aqueous solution. it is particularly preferred thatthe extraction be conducted to yield a final pH in the boron deficientsolution in the range of from about 1 to 6 in order to obtain highestefficiency of boron extraction for most aqueous solutions. Temperatureof the liquids during the extraction step is not critical and istypically in therange of from about 10 to 80 C. lt is most convenient toperform the process at or near room temperature or the ambienttemperature of the aqueous solution source.

After the organic phase and the aqueous phase have been maintained inintimate contact for a sufficient period for the boron to be sequesteredand to partition principally in the organic phase, these phases arepermitted to separate by allowing layers to form and decanting one orboth of such layers. The aqueous layer, now substantially depleted inboron, may be subjected to an additional similar extraction step forfurther depleting the boron or may be otherwise used in commerce in aconventional manner.

The organic phase, which is rich in boron sequestered by the salicylicacid, is then stripped of such boron values by intimately contacting theorganic phase with an aqueous solution of a mineral acid such ashydrochloric, sulfuric, sulfurous, phosphoric, or the like. Distilledwater will also strip boron from the organic phase. The boron valuespartition to the aqueous phase and may be separated therefrom byconventional techniques. Thus, for example, when sulfuric acid isemployed, the stripping aqueous phase may include magnesium sulfate andboric acid in the sulfuric acid solution, and the boric acid may beprecipitated in relatively high purity form. Similarly, if desired, theorganic phase can be stripped of boron values by contacting with analkaline solution, such as, for example, sodium carbonate in order torecover boron in the form of borax; however, this has lower economicvalue in most cases and stripping with mineral acid is preferred.Stripping with alkaline solution results in a salt of the substitutedsalicylic acid derivative, a portion of which may be in the aqueousphase and which could be recovered by neutralization. When the salt isused for extraction, there is less pH change in the boron depletedaqueous phase than when the corresponding acid is present.

The organic phase is substantially free of boron after stripping and ispreferably recycled and reused for additional boron extraction.

The process of extracting boron with the above described salicylic acidderivatives is particulary advantageous in natural brines containingiodine. Catechols and other boron sequestering agents often react withiodine and both the catechol and iodine may be lost. Some natural brinescontain as high as 2 grams per liter of iodine or iodide ion. Processesfor extracting boron from iodine containing brines are satisfactorysince the iodine does not seem to attack the salicylic acid derivativeshereinabove described.

EXAMPLES Boron has been extracted successfully from a mildly acid,iodine-containing, Chilean brine. A typical analysis of this Chileanbrine, which varies somewhat from day to day, because of changes insource is 350 grams per liter of sodium nitrate, 172 grams per liter ofsodium chloride, 58 grams per liter of sodium sulfate, 5.2 grams perliter potassium perchlorate, 30 grams per liter magnesium, 17.9 gramspotassium, and 1.14 grams per liter of iodine. In addition, theconcentration of boric acid is typically in the range of from about 15to 18 grams per liter. The alkalinity of this brine as a sodiumcarbonate equivalent is 2.86, and the pH is typically about 5.0. Thetotal salt concentration of the brine, determined by evaporation at 1 10C, is typically about 607 grams per liter.

In a process for extracting boron from this brine, a water immisciblesolvent comprising 50 percent by volume of Amsco Solvent-G and 50percent by volume of isoamyl alcohol is employed. Dissolved in thissolvent is a sufficient quantity of S-tertiary octyl salicylic acid togive a 0.1 molar solution. (This compound is more explicitly 1,1,3,3,-tetramethyl butyl )-salicylic acid.) Approximately three volumes ofthe above described organic phase are mixed with one volume of brine ina 8 cyclohexyl salicylic acid; 3-isobutyl 5-ethyl salicylic acid;3,5-di-tertiary dodecyl salicylic acid; 5-isooctyl salicylic acid;3-ethyl 5-cyclohexyl salicylic acid, and the like.

vessel equipped for strenuous mechanical agitation so 5 The Series oflaboratory screening tests e forth in that the two phases are broughtinto sufficiently intit g a le emonstrate the synergistic effect of matecontact for sequestering of boron from the aqueisoamyl e e h eothhmehohwith a h Gus phase to the organic phase to OCCUL Average resi tutedsalicylic acid derivative as compared with either dence time of theorganic phase and the brine in the exe y alcehol alone or h derivativealong or m traction vessel is about five minutes; however, this may 10combmaheh h other Qigamc e These data vary depending on the efficiencyof agitation actually were obtained with a brme substantially the sameas achieve that set forth above except for those tests preceded by Themixed aqueous and organic phases are permitted a dquble asterisk whichemployed a bone. acid sqlunon to separate and the two phases areseparately removed. having 1O'67 g/l t acid m water or dilute brine InThis extraction process is repeated four to six times in an of theseScreehmg tests Amsco was a countercurrent manner wherein fresh brine andfresh ployed which an f i h f h extractant flow in opposite directions.In this way the t h cut m hi the salicylic derivative has fresh brinehaving the highest boron concentration is ihsuttieieht eoihhihty for eof the eh as the Sole contacted with the most loaded extractant and theOrganic carrier in the Organic phaee'ftdditiohai g i freshest extractanthaving the greatest sequestering meteiiaie h enhance the Solubility of tSaheyhe power contacts the most depleted brine. A distribution aeitiderivative are therefore Combined w the coefficient of between 0.7 and0.8 is typically observed. matte hi the fohowihg table it will be underAt each successive pass in the countercurrent process Steed that AmseoSOheht'G forms the balance of the 65 to 85 percent of the boron valuesare present in the SOiVeht Portion of the extractant Phase in eachrganic phase In this way from four to ix succes stance, and is thereforenot specifically stated. In the sive contactings, substantially allboron values are reeehlmh headed Extl'aetaht the designation is moved fthe depleted brine employed as an abbreviation for S-tertiary octylsali- The organic phase is then passed in countercurrent eyiie acid- Thedesignation y is p y to flow with mechanical agitation with an aqueoussoluindicate isoamyl aieohei- The designation i tion having at least 10percent sulfuric acid concentradesignates methyl ttioetyi ammoniumChloride which tion. This stripping solution removes boron sequesteredwas Obtained under the trademark q The with the salicylic acidderivative to form a boric acid eeiumh ratio designates the Volume ratioof the solution in the aqueous stripping phase. The boron val- OrganicPhase to the aqueous Phase in the extractionues are precipitated fromthe stripping solution in a The eoiumh labeled P represents the P of theconventional manner. Typically the stripping solution Pieted aqueousbrine after extraction of the bore" also includes sodium, potassium, andmagnesium ions ties y the Organic extractant P in each ease theextracted with the boron from the brine. Typically the P 0f the brinehetol'e extraction was with the amount of such additional ions carriedover is less than eeptioh of those data wherein the P Value is markedabout 70 percent higher than the quantity of boron carwith an asteriskin which cases the P was adjusted to ried over, so that a high degree ofconcentration of the 40 y addition of Sodium hydroxide before theextracboron values as compared with the original brine is obtioh testswere made i In all of these tests, the extractant phase was mechan-Similar results are obtained with water immiscible orically agitatedwith the boron Containing brine for 30 ganic extractant phases includingfrom about 10 to 50 nut s a am i nt p ratur T aqu us and percent or moreof isoamyl alcohol and other water imgarlic PhaseS separated into layersafter agitation, and miscible nuclear substituted salicylic acidderivatives e emoved aqueous layer was filtered and analyzed with atotal of at least 11 carbon atoms in the derivative for ain g r n. Thedata tain d are s t f rth in molecule. Thus, for example, good boronextractions the table in the column headed percent B Extracted." areobtained using procedures and parameters as set The final Column in thetable headed Dist. Coef. forth in the above example when the followingsalicylic gi the distribution f partition C fi ent teracid derivativesare employed in the organic extractant mined by the Weight ratio ofboron in the organic phase phase: S-tertiary butyl salicylic acid;S-tertiary amyl salt0 the bOrOn in the aqueous phase with the datanoricylic acid; S-tertiary nonyl salicylic acid; 3,5-dimalized toaccount for the different volumes of liquids tertiary butyl salicylicacid; S-benzyl salicylic acid; 5; employed inthe various tests. O/A BDist. Extractant Ratio pH Extracted Coef.

50% n-butanol 2.5 5.6 25 0.133 25% n-butanol 5 5.7 31 0.090 50%2-octanol 2.5 5.5 26 0.141 25% Z-octanol 5 5.6 32 0.094 50% isodecanol 5"7.3 33 0.099 25% isodecanol 5 *7.3 26 0.070 50% isodecanol 2.5 6.2 480.369 50% isodecanol 5 6.3 63 0.34] 25% isodecanol 5 6.0 5l 0.208 50%isoamyl 5 5.4 25.2 0.068 50% isoamyl 2 5.7 28.8 0.202 50% isoamyl 5 6.560.1 0.307 25% isoamyl 2 V H 5.Y9 38.0 0.306

:Q9nt 1mm4 O/A B Extractant Ratio pH Extracted 25% isoamyl m '5 ""613"5712' 0.4M OSA+50% isodecanol 2.5 3.0 55

0.lM SA+50% isodecanol 2.5 4.3 56

0.1M OSA+50% isodecanol 4.2 7l

0.1M OSA+50% isodecanol L5 4.6 43

0.2M 0SA+25% isodecanol 5 3.7 62

0.05M OSA+% isodecanol 5 4.6 63

0.1M 0SA+25% isoamyl 2 4.3 48.0

0.1M OSA+2S% isoamyl 3 4.3 59.3

0.1M OSA+25% isoamyl 4 4.] 65.6

0.1M OSA+25% isoamyl 5 4.l 71.0 0.490

0.1M 0SA+50% isoamyl 2 4.5 58.3 0.699

0.lM GSA-+50% isoamyl 3 4.2 68.7 0.732

0.lM OSA+50% isoamyl 4 4.2 74.0 0.712

0.1M OSA+50% isoamyl 5 2.8 77.5 0.688 0.lM 0SA+25% isoamyl 2 4.9 17.50.106 0.1M OSA-l-ZSV: isoamyl 5 5.0 32.5 0.096 0.lM OSA+50% isoamyl 25.3 24.7 0.l64 0.1M 0SA+50% isoamyl 5 5.3 44.l 0.158 0.lM GSA-+50%isoamyl 5 5.1 43.6 0.155

0.1M OSA+.|M Aliq.+507z isoamyl 5 2.7 75.0 0.600 0.1M OSA+.IM Aliq.+50%isoamyl 5 1.4 48.9 0.191

0.1M OSA+0.lM Aliq.+50% isodecanol 2.5 3.8 56 0.509

2M OSA+6% 2-octanol The data set forth in the above table showathatisodecanol and isoamyl alcohol are approximately comparable in theability to extract boron from brine. nbutanol and 2-octanol are inferiorto either isodecanol or isoamyl alcohol. Surprisingly, however, when thesalicylic acid derivative is combined with a solvent including isoamylalcohol, a much higher boron extraction is obtained than when thesalicylic acid derivative is added to a solvent including isodecanol.The reason for the synergistic effect of isoamyl alcohol and thesalicylic acid derivative is not known.

Similar good results are obtained with other nuclear substitutedsalicylic acid derivatives in combination with isoamyl alcohol inorganic phases as set forth in the following table.

Salicylic Acid (SA) monium salt thereof, in the solvent, said nuclearsubstituted salicylic acid having the formula W COOH OH R R s mg l yi ihabsea -anslel ylsr yns sa Concen Derivative tration Organic Solvent3,5-di-tertiary butyl SA 0.2M Amsco G. 50% isoamyl alcohol S-tertiaryamyl SA 0.1M do. S-tertiary nonyl SA 0.1M do. 3-ethyl-5 cyclohexyl SA0.15M do. 3-amyl-5 tertiary octyl SA 0.1M do. 3-isobutyl-5 ethyl SA 0.lMdo. 3,5-di-tertiary nonyl SA 0.l do. Zy! L 2 -L "Q" '3,S-di-tertiarydecyl SA Til d 3-isopropyl-6 methyl SA 0.1 do. 3-chloro-5 tertiary octylSA 0.1 do.

Although limited examples of extractions embodying principles of thisinvention have been set forth in detail herein, it will be understoodthat many modifications .and variations can be made by one skilled inthe art. It is, therefore, to be understood that within the scope of theappended claims the invention may be practiced otherwise than asspecifically described.

What is claimed is:

l. A composition comprising:

a substantially water immiscible organic solvent comprising from 10 to100 percent by volume of isoamyl alcohol; and

at least 0.05 molar concentration of substantially water immiscible,nuclear substituted salicylic acid or alkali, alkaline earth, ammoniumor organica l- COOH 3. A composition as defined in claim 2 wherein theradical R is a tertiary alkyl radical containing from 8 to 1 rbsmawm 4composition as defined in claim 2 wherein the 000E salicylic acid orsalt thereof has less than about 40 carbon atoms. v .M r2 H 5. Acomposition as defined m claim 1 wherein the R solvent further comprisesup to about 90 percent by 5 volume of a water immiscible petroleumfraction.

6. A composition as defined in claim 1 wherein isoamyl alcohol ispresent in the solvent in a proportion up A Composition as defined inClaim 8 wherein the to about 50 percent by volume. solvent furthercomprises up to about 75 percent by 7. A composition as defined in claim6 wherein iso- 10 volume of a water immiscible petroleum fraction. amylalcohol is present in the solvent in a proportion 10. A composition asdefined in claim 9 wherein the greater than about 25 percent by volume.radical R is a tertiary alkyl radical containing from 8 to 8. Acomposition as defined in claim 7 wherein the 12 cal-bon atoms 1salicylieacidor salt thereof has the formula i p 7* 'o ED S'f/ITEsPATENT OFFICE I CERTIFICATE OF CORRECTION Patent Nov 3.839.222 DatedOctober 1..- 1974 Inventot(S) 4 Edward A. Grarmen It is certified thaterror appears in the above-idiitified patent and that said Letter-sPatent are hereby corrected as showubelow:

In the heading, I Item [76] should read Assignee: Occidental PetroleumCorporation, Los Angeles, California;

Claim 8, colurrin' -lZ line 3, the formula should be;

\ ,OH. I

signed and sealed this 31st dayof Deoember 1974.

(SEAL) Attest:

McCOY M; GIBSON JR. (2'. l-LARSHALL DANN attesting Officer Commissionerof Patents V 221 .3 a i UNITED S'fA'rI-is PATEN' If O I CERTIFICATE ORECTION Patent NO- 3.839.222 Dated October 1. 1974 Inventor(S) '1 EdwardA. Grannen It is certified that error appears in the above-idhtifiedpatent and that said Letters Patent are hereby corrected as shown-below:v

In the heading, Item [76] should read Assignee: Occidental PetroleumCorporation, Los Angeles, California; 2

Claim 8 colum n '12 line 3, the formula should be Signed and sealed this31st dayof D'ece mb er 19-74.

(SEAL) Attest:

McCOY MI GIBSON JR. 0. MARSHALL DANN Attestirxg Officer Commissioner ofPatents

1. A COMPOSITION COMPRISING: A SUBSTANTIALLY WATER IMMISCIBLE ORGANICSOLVENT COMPRISING FROM 10 TO 100 PERCENT BY VOLUME OF ISOAMYL ALCOHOL;AND AT LEAST 0.05 MOLAR CONCENTRATION OF SUBSTANTIALLY WATER IMMISCIBLE,NUCLEAR SUBSTITUTED SALICYCLIC ACID OR ALKALI, ALKALINE EARTH, AMMONIUMOR ORGANIC AMMONIUM SALT THEREOF, IN THE SOLVENT, SAID NUCLEARSUBSTITUTED SALICYCLIC ACID HAVING THE FORMULA
 2. A composition asdefined in claim 1 wherein the salicylic acid or salt thereof has theformula
 3. A composition as defined in claim 2 wherein the radical R isa tertiary alkyl radical containing from 8 to 12 carbon atoms.
 4. Acomposition as defined in claim 2 wherein the salicylic acid or saltthereof has less than about 40 carbon atoms.
 5. A composition as definedin claim 1 wherein the solvent further comprises up to about 90 percentby volume of a water immiscible petroleum fraction.
 6. A composition asdefined in claim 1 wherein isoamyl alcohol is present in the solvent ina proportion up to about 50 percent by volume.
 7. A composition asdefined in claim 6 wherein isoamyl alcohol is present in the solvent ina proportion greater than about 25 percent by volume.
 8. A compositionas defined in claim 7 wherein the salicylic acid or salt thereof has theformula
 9. A composition as defined in claim 8 wherein the solventfurther comprises up to about 75 percent by volume of a water immisciblepetroleum fraction.
 10. A composition as defined in claim 9 wherein theradical R is a tertiary alkyl radical containing from 8 to 12 carbonatoms.